Preparation device of halogenated butyl rubber basic glue solution

Abstract

The utility model discloses a preparation device of a halogenated butyl rubber basic glue solution. The device comprises a dissolving column and a water removal unit, the dissolving column is at least provided with a colloidal particle and water material inlet and a solvent material inlet which are used for respectively introducing colloidal particle and water material flow containing butyl rubber particles and water and solvent material flow; after the colloidal particle water material flow is contacted with the solvent material flow in the dissolving column, an oil phase and a water phase in which butyl rubber particles are dissolved are formed; a water phase outlet is formed in the bottom of the dissolving column and is used for discharging a water phase; an oil phase outlet is formed in the upper part of the dissolving column and is used for discharging an oil phase dissolved with butyl rubber particles; the oil phase outlet is connected with the water removal unit, and the water removal unit is used for removing free moisture in the oil phase in which butyl rubber is dissolved to obtain a butyl rubber basic rubber solution. The device disclosed by the utility model is low in energy consumption, energy-saving, environment-friendly and beneficial to industrial realization.

Description

[0001] This application claims priority to a prior application, patent application number 2024112273696, filed with the State Intellectual Property Office of China on September 3, 2024, entitled “A Method and Apparatus for Preparing a Halogenated Butyl Rubber Base Solution.” The entire text of the prior application is incorporated herein by reference. Technical Field

[0002] The utility model belongs to the technical field of halogenated butyl rubber preparation devices, and in particular relates to a preparation device for a butyl rubber base adhesive solution for halogenation. Background Art

[0003] Isobutylene and a small amount of isoprene are polymerized at around -100°C via a low-temperature slurry process using methyl chloride as a diluent to produce basic butyl rubber. This basic butyl rubber is dissolved in an alkane to produce a butyl rubber base solution. This base solution then reacts with a halogen. The resulting halogenated product is then subjected to hydrolysis, coagulation, and drying to produce halogenated butyl rubber. Halogenated butyl rubber is currently the primary raw material for tire innerliners.

[0004] Currently, the industry generally uses a process for preparing halogenated butyl rubber base liquid by coagulating and resolubilizing low-temperature slurry with hot water. First, the low-temperature slurry produced by the butyl rubber polymerization reactor is mixed with a catalyst, terminator, steam, and other heat sources and then fed into a degassing reactor. Methyl chloride is stripped out, and the precipitated butyl rubber particles are simultaneously mixed with water to form a pelletized solution containing approximately 5 wt%. The pelletized solution is then subjected to vibratory screening, screw extrusion for dehydration, and pelletization. Afterwards, it is fed into a dissolving tank and mixed with hexane to dissolve the resulting solution, which is then dehydrated to prepare the halogenated butyl rubber base liquid. This process has the disadvantages of multiple steps and a long route.

[0005] CN111548436A discloses a method for preparing a butyl rubber base solution for a halogenation reaction. The method involves mixing a butyl rubber slurry with a solvent, a terminator, and a diluent to obtain a butyl rubber mixed solution containing methyl chloride, unreacted monomers, and the solvent after the reaction is terminated. The butyl rubber mixed solution is then subjected to flash evaporation and concentration to remove methyl chloride, unreacted monomers, and the like, resulting in a butyl rubber base solution of suitable concentration. This "solvent exchange process" also has the disadvantages of a long process and high energy consumption. Utility Model Content

[0006] In order to improve the above technical problems, the utility model provides a device for preparing a butyl rubber base solution for halogenation, the device comprising a dissolving column and a water removal unit;

[0007] The dissolving column is provided with at least a colloidal water material flow inlet and a solvent material flow inlet, for respectively introducing the colloidal water material flow and the solvent material flow containing butyl rubber particles and water; after the colloidal water material flow and the solvent material flow come into contact in the dissolving column, an oil phase and a water phase containing dissolved butyl rubber particles are formed;

[0008] The bottom of the dissolution column is provided with a water phase outlet for discharging the water phase;

[0009] The upper portion of the dissolving column is provided with an oil phase outlet for discharging the oil phase containing the dissolved butyl rubber particles;

[0010] The oil phase outlet is connected to the water removal unit, which is used to remove free water in the oil phase containing butyl rubber to obtain a butyl rubber base solution.

[0011] According to the embodiment of the present utility model, the inlet of the water material flow of the colloid particles on the dissolution column is connected to the butyl rubber colloid particle water pipeline, and the inlet of the solvent material flow is connected to the solvent pipeline.

[0012] According to an embodiment of the present invention, the colloidal water stream is added from the middle and lower part of the dissolution column.

[0013] According to an embodiment of the present invention, the solvent stream is added from the middle and lower part of the dissolution column.

[0014] According to an embodiment of the present invention, the colloidal water stream and the solvent stream are added from different inlets in the middle and lower part of the dissolution column.

[0015] According to an embodiment of the present invention, the water removal unit includes a water separator. The water separator is used to remove water from the oil phase containing the butyl rubber. The oil phase is further separated into a water-free oil phase and a water phase in the water separator. The water-free oil phase is the final butyl rubber base solution.

[0016] According to an embodiment of the present invention, the water removal unit further comprises an oil phase cooler, which is located between the oil phase outlet of the dissolution column and the water separator, and the oil cooler is used to cool the oil phase containing butyl rubber.

[0017] According to an embodiment of the present invention, the water separator is further connected to a dehalogenation reaction unit. The dehalogenation reaction unit is used for further halogenation of the butyl rubber base solution.

[0018] According to an embodiment of the present utility model, the water phase outlet of the dissolution column is connected to a water phase temporary storage tank, and the water phase temporary storage tank is used to collect the water phase.

[0019] According to an embodiment of the present invention, the water phase temporary storage tank is connected to a water phase distillation tower, and the water phase distillation tower is used to separate the solvent in the water phase to obtain a solvent-reduced water phase.

[0020] According to an embodiment of the present invention, the bottom end of the water separator is also connected to the top end of the water phase temporary storage tank via a pipeline. After removing water from the oil phase containing butyl rubber in the water separator, the resulting water is fed into the water phase temporary storage tank.

[0021] According to an embodiment of the present invention, the dissolution column is selected from one of a plate column, a packed column or a bubble column, or a combination of two or three thereof.

[0022] According to an embodiment of the present invention, the device further comprises a butyl rubber polymerization unit, and the butyl rubber polymerization unit is connected to the dissolution column.

[0023] According to an embodiment of the present utility model, the bottom end of the water phase distillation tower is also connected to a butyl rubber polymerization unit.

[0024] According to the embodiment of the present utility model, the butyl rubber polymerization unit at least includes a butyl rubber polymerization kettle and a water separation and coagulation unit; the butyl rubber polymerization kettle and the water separation and coagulation unit are connected, and the water separation and coagulation unit is connected to the dissolution column.

[0025] According to an embodiment of the present invention, the bottom end of the aqueous phase distillation column is also connected to a water separation and coagulation unit. The aqueous phase with reduced solvent is returned to the water separation and coagulation unit in the butyl rubber polymerization unit and used as coagulation circulating hot water.

[0026] Beneficial effects of the utility model:

[0027] The utility model provides a device for preparing a butyl rubber base solution with a short process (short route) and low energy consumption. The device directly contacts the colloidal water with the solvent in a dissolving column, achieving rapid oil-water separation. A qualified butyl rubber base solution is obtained in just two steps, significantly shortening the process route. Furthermore, the process has low energy consumption, is energy-saving, and is environmentally friendly, making it conducive to industrialization.

[0028] In addition, the content of butyl rubber particles in the colloidal water is generally around 3-10%, containing a large amount of water. After the colloidal water is mixed and contacted with the solvent, the separated aqueous phase contains a small amount of solvent. If directly discarded, it will result in waste of raw materials and increase industrial production costs. However, if the solvent is not removed and it is directly reused as circulating hot water in the butyl rubber polymerization unit, it will have a negative impact on the butyl rubber polymerization unit. The utility model treats the aqueous phase, removes the solvent, and uses the resulting solvent-reduced aqueous phase as condensation circulating hot water for the butyl rubber polymerization unit (specifically, for the water separation and condensation unit of the butyl rubber polymerization unit), greatly reducing production costs, reducing emissions and increasing efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a diagram of the device of the utility model;

[0030] Among them: 1. Butyl rubber granule water pipeline, 2. Solvent pipeline, 3. Dissolution column, 4. First pipeline, 5. Second pipeline, 6. Oil phase cooler, 7. Water separator, 8. Basic rubber solution, 9. Water phase temporary storage tank, 10. Water phase distillation tower, 11. Solvent-reduced water phase, 12. Solvent. DETAILED DESCRIPTION

[0031] The following will further describe the technical solutions of the present invention in conjunction with specific embodiments. It should be understood that the following embodiments are merely illustrative and explain the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included within the scope of protection intended by the present invention.

[0032] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0033] Example 1

[0034] A device for preparing a halogenated butyl rubber base liquid, comprising: a dissolving column 3, to which a butyl rubber colloidal water pipeline 1 and a solvent pipeline 2 are connected, respectively connected to a colloidal water inlet and a solvent inlet, for respectively introducing colloidal water containing butyl rubber particles and water and solvent.

[0035] The upper part of the dissolution column is provided with an oil phase outlet, which is connected to a water removal unit; the water removal unit includes an oil phase cooler 6 and a water separator 7 connected in sequence; the oil phase cooler 6 is used to cool the oil phase containing butyl rubber; in the water separator 7, the cooled oil phase containing butyl rubber is separated into an oil phase and water, and the oil phase is the butyl rubber base rubber solution 8.

[0036] The bottom of the dissolution column is provided with a water phase outlet, which is sequentially connected to a water phase temporary storage tank 9 and a water phase distillation tower 10; the water phase temporary storage tank 9 is used to collect the water phase; the water phase distillation tower 10 is used to separate the solvent in the water phase to obtain a solvent-reduced water phase.

[0037] The bottom end of the water separator is also connected to the top end of the water phase temporary storage tank through a pipeline. After removing water from the oil phase containing butyl rubber in the water separator, the obtained water is sent to the water phase temporary storage tank.

[0038] The butyl rubber polymerization unit includes a butyl rubber polymerization kettle (not shown in the figure) and a water separation and coagulation unit (not shown in the figure); the butyl rubber polymerization kettle and the water separation and coagulation unit are connected, and the water separation and coagulation unit is connected to the dissolution column.

[0039] The bottom end of the water phase distillation tower is connected to the water separation and coagulation unit. The water phase with reduced solvent is returned to the water separation and coagulation unit in the butyl rubber polymerization unit and used as coagulation circulating hot water.

[0040] Specifically, the operation mode of the device is:

[0041] After the colloidal water stream and the solvent stream come into contact within the dissolution column 3, the solvent dissolves the butyl rubber in the colloidal water, resulting in an oil phase containing butyl rubber and an aqueous phase. The oil phase containing butyl rubber exits the column top via a second pipeline 5. The oil phase is temperature-adjusted in an oil phase cooler 6 and then enters a water separator 7 to separate out entrained free water. The resulting base rubber solution 8 is then transported via a pipeline to a dehalogenation reaction unit. The aqueous phase, which is obtained at the bottom of the dissolution column 3 due to its high density, exits the bottom of the dissolution column 3 and enters a temporary aqueous phase storage tank 9 via a first pipeline 4. The temporary aqueous phase then passes through an aqueous phase distillation tower 10, where the remaining solvent is distilled and recovered, yielding a solvent-reduced aqueous phase 11. This solvent-reduced aqueous phase 11 can be returned to the butyl rubber polymerization unit for use as circulating hot water in the hydrolysis and coagulation unit. Simultaneously, the distilled solvent 12 is recovered.

[0042] Example 2

[0043] This embodiment is a method for preparing a halogenated butyl rubber base solution based on the device, and the method at least includes (A) to (C):

[0044] (A) preparing or providing a pelletized water stream comprising butyl rubber particles and water;

[0045] (B) contacting the colloidal water stream with a solvent stream to obtain an oil phase and an aqueous phase containing butyl rubber;

[0046] (C) removing the solvent dissolved in the aqueous phase in step (B) to obtain a solvent-reduced aqueous phase.

[0047] In one embodiment, the method further comprises step (D):

[0048] (D) removing water from the oil phase containing the butyl rubber in step (B) to obtain a butyl rubber base solution.

[0049] In one embodiment, the method further comprises step (E):

[0050] (E) The solvent-reduced aqueous phase obtained in step (C) is returned to the butyl rubber polymerization unit and used as condensation circulating hot water.

[0051] In one embodiment, in step (C), the method for removing the solvent dissolved in the aqueous phase in step (B) is one or a combination of flash evaporation, distillation, and stripping.

[0052] In one embodiment, the butyl rubber polymerization unit comprises at least a butyl rubber polymerization kettle and a water separation and coagulation unit, and the aqueous phase with reduced solvent in step (C) is returned to the water separation and coagulation unit in the butyl rubber polymerization unit and used as coagulation circulating hot water.

[0053] In one embodiment, in step (A), the content of butyl rubber particles in the rubber water is 3-10 wt %, illustratively 3, 4, 5, 6, 7, 8 wt %, 9 wt % or 10 wt %.

[0054] In one embodiment, in step (A), the colloidal water is prepared using existing methods. For example, it can be prepared by the butyl rubber polymerization unit. Exemplarily, it can be obtained by the following method: low-temperature slurry produced by a butyl rubber polymerization kettle is mixed with a catalyst, terminator, steam, and other heat sources, and then introduced into the coagulation kettle of a water separation and coagulation unit. Methyl chloride is stripped out, and the precipitated butyl rubber particles are mixed with water to form the colloidal water. Alternatively, the colloidal water can be obtained by mixing butyl rubber particles with water.

[0055] In one embodiment, step (B) is performed in a dissolution column. Specifically, the dissolution column is selected from a plate column, a packed column, or a bubble column, or a combination of two or three thereof.

[0056] In one embodiment, in step (B), the mass ratio of the colloidal water to the solvent is (2-6):1, for example, 2:1, 3:1, 4:1, 5:1 or 6:1.

[0057] In one embodiment, the operating pressure of the dissolution column is 80 kPa-500 kPa; preferably 100 kPa-400 kPa.

[0058] In one embodiment, the operating temperature of the dissolution column is 25-90°C, preferably 40-80°C.

[0059] In one embodiment, the colloidal water stream is contacted with the solvent stream in a dissolution column with a residence time of 0.3 to 1.5 hours.

[0060] In one embodiment, in step (B), the colloidal water stream is added from the middle and lower part of the dissolution column.

[0061] In one embodiment, in step (B), the solvent stream is added from the middle and lower part of the dissolution column.

[0062] In one embodiment, in step (B), the colloidal water stream and the solvent stream are added from different inlets in the middle and lower part of the dissolution column.

[0063] In one embodiment, in step (B), the aqueous phase contains a certain amount of solvent, specifically, the content of the solvent is 0.01-0.03% wt, preferably 0.01-0.02% wt.

[0064] In one embodiment, in step (D), when removing water from the oil phase containing butyl rubber in step (B), the temperature of the oil phase is 10-50°C. Specifically, the oil phase containing butyl rubber from step (B) is cooled before removing free water therefrom. Specifically, the cooling is performed in an oil phase cooler.

[0065] In one embodiment, in step (D), the cooled oil phase is dehydrated in a water separator. Specifically, the oil phase is further separated into a water-free oil phase and a water phase in the water separator, wherein the water-free oil phase is the final butyl rubber base solution.

[0066] In one embodiment, in step (D), the butyl rubber base solution is sent to a halogenation reaction unit.

[0067] In one embodiment, the separated water in step (D) can be combined with the water phase in step (B), or used in the butyl rubber polymerization unit, specifically, in the water separation and coagulation unit in the butyl rubber polymerization unit.

[0068] In one embodiment, in step (E), all or part of the solvent-reduced aqueous phase is returned to the butyl rubber polymerization unit.

[0069] Example 3

[0070] This example was carried out in the equipment of Example 1.

[0071] The butyl rubber base rubber crumb water obtained from the isobutylene and isoprene copolymerization unit is 7351 kg / h, containing 6.65% butyl rubber and at a temperature of 65°C. The crumb water enters the dissolution column 3 from the middle and lower part. The dissolution column 3 is a free plate column with a column volume of 9m 3 Column 3 has a diameter of 800 mm. 1350 kg / h of 50°C n-pentane enters dissolution column 3 from the lower middle portion, with the n-pentane inlet opposite the colloidal water inlet. The temperature inside dissolution column 3 is 63°C, the column pressure is 370 kPa, and the residence time inside the column is 1 hour.

[0072] The oil phase out of the top of dissolution column 3 is an oil phase containing butyl rubber, which contains a certain amount of water. The oil phase is cooled to 40°C, and the water is separated in the water separator to obtain 1916.5 kg / h of basic rubber solution, which is transported to the dehalogenated butyl rubber reaction unit.

[0073] The water phase at the bottom of the dissolution column 3 contains 0.01-0.02% wt of solvent, which is distilled and separated in the distillation tower 10 to obtain 6860 kg / h of solvent-reduced water phase, which is all returned to the butyl rubber polymerization unit.

[0074] The above describes exemplary embodiments of the present invention. However, the scope of protection of the present invention is not limited to the aforementioned embodiments. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A device for preparing a halogenated butyl rubber base solution, characterized in that: The device includes a dissolving column and a water removal unit; The dissolving column is provided with at least a colloidal water material flow inlet and a solvent material flow inlet, for respectively introducing the colloidal water material flow and the solvent material flow containing butyl rubber particles and water; after the colloidal water material flow and the solvent material flow come into contact in the dissolving column, an oil phase and a water phase containing dissolved butyl rubber particles are formed; The bottom of the dissolution column is provided with a water phase outlet for discharging the water phase; The upper portion of the dissolving column is provided with an oil phase outlet for discharging the oil phase containing the dissolved butyl rubber particles; The oil phase outlet is connected to the water removal unit, which is used to remove free water in the oil phase containing butyl rubber to obtain a butyl rubber base solution.

2. The device according to claim 1, characterized in that The inlet of the colloid water material flow on the dissolution column is connected to the butyl rubber colloid water pipeline, and the inlet of the solvent material flow is connected to the solvent pipeline.

3. The device according to claim 1, characterized in that The water removal unit includes a water separator.

4. The device according to claim 3, characterized in that The dewatering unit includes a water separator and an oil phase cooler. The oil phase cooler is located between the oil phase outlet of the dissolution column and the water separator. The oil phase cooler is used to cool the oil phase containing butyl rubber.

5. The device according to claim 3 or 4, characterized in that The water separator is also connected to the dehalogenation reaction unit.

6. The device according to claim 1, characterized in that The water phase outlet of the dissolution column is connected to a water phase temporary storage tank, and the water phase temporary storage tank is used to collect the water phase.

7. The device according to claim 6, characterized in that The water phase temporary storage tank is connected to a water phase distillation tower, and the water phase distillation tower is used to separate the solvent in the water phase to obtain a solvent-reduced water phase.

8. The device according to claim 6, characterized in that The aqueous phase temporary storage tank is connected to an aqueous phase distillation tower, which is used to separate the solvent in the aqueous phase to obtain an aqueous phase with reduced solvent. The water removal unit includes a water separator, and the bottom end of the water separator is also connected to the top end of the aqueous phase temporary storage tank through a pipeline.

9. The device according to claim 8, characterized in that The device further comprises a butyl rubber polymerization unit, which is connected to the dissolving column.

10. The device according to claim 7 or 8, characterized in that The bottom end of the water phase distillation tower is also connected to a butyl rubber polymerization unit.

11. The device according to claim 9, characterized in that The butyl rubber polymerization unit at least includes a butyl rubber polymerization kettle and a water separation and coagulation unit; the butyl rubber polymerization kettle and the water separation and coagulation unit are connected, and the water separation and coagulation unit is connected to the dissolution column.

12. The device according to claim 11, characterized in that The bottom end of the water phase distillation tower is also connected to a water separation and condensation unit.

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